Method of preparing hydroxy heavy metal soap compositions



Patented Jan. 30, 1945 METHOD OF PREPARING ROXY HEAVY METAL SOAPCOMPOSITIONS Arthur Minich, Westfield, N. J.

No Drawing. Application May 1'7, 1944,.

Serial No. 536,022

3 Claims.

This invention relates to a method of preparing mixtures of hydroxymetal soaps in vehicles and while capable of use in the production ofsoaps of various metals, is especially useful in the preparation ofhydroxy copper naphthenates alone or in combination with other metallicsoaps including normal copper naphthenates. Thus it is possible toobtain, for example, hydroxy copper naphthenate soaps of practically anydesired hydroxy content.

In my previous Patent No. 2,116,321, dated May 3, 1938, I described thepreparation of hydroxy metal soaps including hydroxy copper naphthenatein such manner that the end product was generally in dry pulverulentform. This required, in the course of the incorporation of such hydroxymetal soaps into other compositions, mechanical grinding or other steps,so as 'to bring about proper dispersion of the hydroxy soap in theassociated composition. This procedure is attendant with certaindiificulties. It i well known that grinding of pulverulent matter is alaborious and relatively expensive operation and often requires specialapparatus including dust collecting apparatus, etc. Furthermore, theproduction of the hydroxy metal soaps in pulverulent form requiresdrying equipment of relatively large floor area and the drying operationusually requires a protracted time cycle. Following the drying, thehydroxy metal soap has to be comminuted by such means as grinders,

sifters, etc. in order to yield a substantially uni-' form pulverulentmaterial. In addition to these drawbacks, it is also necessary to selectthe raw material component carefully, so that the resultant compositionis non-sticky, and will not tend to agglomerate. Moreover it isnecessary that water remaining from the double decomposition reaction besubstantially removed in order to permit the proper functioning of theend product. This has been accomplished by mechanical drying.

I have found that all of the above mentioned disadvantages accruing tothe production and use of pulverulent hydroxy metal soaps, may besubstantially eliminated through the employment of the present inventionnext to be described.

In carrying out the present invention in its preferred practical form, Iemploy three solutions A, B and C: Solution A representing an aqueoussolution of an alkali soap of a predetermined organic water-insolubleacid, together with free and unreacted alkali hydroxide, and Solution Brepresenting an aqeous solution of the watersoluble salt of the selectedheavy metal. When these two solutions are brought together underagitation, there is formed the hydroxy metal soap of such metal andacid. This hydroxy metal soap precipitates out in the form of awater-insoluble magma. It is separated from the by-product salts and alarge portion of the water by mechanical means, such as filter pressing.The magma may also receive subsequent water washings to free it entirelyfrom the by-product salts.

It is also within the purview of this invention to eliminate at thisstage of the method the removal of any of the water and/or the saidbyproduct salts.

Following this the magma is then mixed under agitation with Solution Cwhich is preferably wholly or in part volatile. Ordinarily it ispreferred to employ for this purpose a vehicle including a volatilesolvent because this aids in the subsequent removal of water.

The vehicle employed may be selected from a broad range. For example, Ihave found it very satisfactory to employ as a vehicle a petroleumsolvent, known under the trade name Sovasol. Likewise, I havesatisfactorily employed coal tar hydrocarbons, e. g., xylol.

The solvent may be selected from the broad class of organicsubstantially water-insoluble liquids which are employed in the arts,generally, as solvents, such as paint solvents, rubber solvents, etc.They are not necessarily a solvent for the hydroxy metal soaps formingpart of the magma to which I have referred.

The mixture of the hydroxy metal soap magma in said vehicle is thereuponsubjected to the action of heat to effect a dehydration operation. Thismay be carried out at atmospheric pressure or in vacuo, and I have foundthat under these conditions, the water present in the hydroxy metal soapmagma will distill off readily and completely, leaving behind thehydroxy metal soap in finely dispersed form in the vehicle.

It is necessary during the dehydration operation that there iscontinually present a part or all of the vehicle associated with thehydroxy metal soap so that, as the operation proceeds, the soap becomethoroughly dispersed through-v out the vehicle. Aside from this criticalfactor, the actual amount of vehicle employed may vary within widelimits depending upon conditions. It has been found expedient in somecases to return continuously to the reaction apparatus those portions ofthe volatile vehiclewhich distill off with the water, so as to maintainwithin the reaction kettle substantially uniform conditions.

The material produced at the conclusion of the dehydration or dryingstep may contain different amounts of vehicle, so as to be in the formof a. relatively thick paste or in the form of a pourable liquid,depending upon what is desired for particlar uses, or if it comes fromthis operation in the form of a thick paste, it may be diluted withfurther amounts of the vehicle as it may be desired. In any event, thedegree of dispersion attained by the procedure of this invention issuperior to that which may be obtained by mechanically dispersing thepulverulent hydroxy metal soap in the same vehicle.

I have referred to the production of a soap of a single metal duringdouble decomposition steps described. I may, however, if so desiredeffect double decomposition of a plurality of metals at the same timeor, if desired, Imay carry out double decomposition as described for onemetal and also the same steps in connection with one or more additionalmetals, and thereafter commingle or bring together the resulting magmaof the several metals before jointly dehydrating them in the drying stepwhich I have described.

I have also referred to the use of a waterinsoluble organic acid, in theproduction of the hydroxy metal soap according to this invention. I donot limit this invention to the use of a single acid alone, but mayemploy a plurality of such acids for this purpose. The acids employedare, however, substantially waterinsoluble and substantiallynon-volatile and should be such as to form the water-insoluble hydroxymetal soaps. They can be aromatic acids, such as para-chlorbenzoic acid,aliphatic acids, such as oleic acid, linseed oil fatty acids, and cyclicacids, such as naphthenic acid. Tall oil may also be used for thispurpose.

The formation of the hydroxy metal soap in form of its water magma hasbeen described as the initial process step of this invention. It ispossible, however, to precipitate first either a hydroxy metal soap ofgreater basicity than is desired in the dehydrated product or it is alsofeasible to precipitate the straight hydroxide of the metal. In thesecases, it is possible to include in the vehicle employed in drying, asufficient amount of the organic acid to react with the metal hydroxideor hydroxy metal soap of the metal present, so as to bring about thedesired hydroxy content of the dehydrated product.

The production of a wide variety of metal soaps may be accomplished bythe method of this invention according to the metals which enter intothe reaction. For example, I may use such metals as copper, zinc, lead,cobalt, manganese, iron and generally the other heavy metals which arecapable of forming water-insoluble hydroxides.

For the purpose of concrete example, I shall now describe the productionof a hydroxy copper naphthenate soap useful for various purposes, butmore particularly as a fungicidal and insecticidal agent. This compoundmay also form a component part of orchard sprays for pest control.

EXAMPLE 1 Solution A droxy metal naphthenate in the vehicle.

Solution 8 Pound: Copper sulphate crystals (25% copper) 190 Water 70CSolutions A and B were commingled under agitation. The hydroxy coppernaphthenate which was formed precipitated out in the form of awater-insoluble magma. The entire reaction mixture was then filterpressed to remove the larger portion of the water. The hydroxy metalsoap magma remaining in the filter press was washed to remove theby-product salts. The hydroxy metal soap magma containing approximately70% water was then incorporated under agitation into the followingvehicle which may be referred to as:

Solution C Pounds Sovasol (a volatile petroleum distillate solventmanufactured by The Standard Oil Co. of New York) 200 The mixture ofSolution C with the hydroxy metal naphthenate magma was heated underagitation in a closed kettle to a temperature of approximately C. Thewater was thus distilled off together with a portion of the volatilepetroleum distillate solvent, a part of which solvent upon condensationwas fed back into the kettle.

The foregoing example contained 259 lbs. less naphthenic acid than thenormal compound would require. On a percentage basis, it contained 33%of the amount required to form the normal compound.

The dehydration of the hydroxy metal naphthenate soap during thisdehydration step was so complete that upon completion, there was presentless than 1% of water in the end product. The end product, in theapproximate amount of 264 lbs., constituted a mobile mixture of the hy-The consistency was that of a heavy, but flowable liquid. Theconcentration of the hydroxy metal soap was 70% (metal contentapproximately 8%), the balance being the petroleum distillate solvent.

It was particularly notable that in the end product, the resultingmixture of the metallic soap was practically of colloidal fineness indispersed form-in fact, much finer and complete than could possibly beobtained by mechanical means. This is an important factor because,generally speaking, the efliciency of many compositions, particularlyfungicides, depends upon very fine state of dispersion.

It is to be noted that the end product is a true hydroxy coppernaphthenate because it has been formed through the double decompositionof copper sulphate with the combination of alkali naphthenate soap andfree alkali hydroxide. More specifically, inthe reaction referred to,there was present approximately pounds of free and unreacted aqueoussodium hydroxide solution of oi the acid to be employed in Solution Aand the remainder in Solution C, the condition being in every case thatthe total amount 01' organic acid employed is insumcient to form thenormal compound and therefore perforce the hydroxy compound must beformed. As exemplary oi the latter procedure, note the following:

Pounds Water 1,200 Aqueous solution of caustic soda of 25% strengthnaphthenic acid than the normal compound would require. On a percentagebasis, it contained 33% of the amount required to form the normalcompound.

Yield of the composition: approximately 264 lbs. of dispersion te,containing 70% total solids-18% copper.

The advantage of the procedure of this example is that the physicalbulking of the hydroxy metal soap magma in the filter press is reducedby the omission of part oi. the organic acid and this means that asmaller bulk including less water need be handled in the filter presses.

The naphthenic acid which forms part of Solution C reacts completelythrough the dehydration cycle, so that the end product, namely, thehydroxy copper naphthenate, is identical in composition with the copperhydroxy naphthenate of Example 1 wherein the total amount of naphthenicacid was present during the magma formation.

In the process of dehydration, sufllcient xylol is removed with thewater distilling ed to yield 265 lbs. of a paste composition containingap proximately 64% of the hydroxy soap-15% copper.

The composition represents a dispersion ofhydroxy copper oleate in amixed vehicle.

The formula contains 228 pounds oieic acid less than the normal compoundwould require and on a percentage basis, it, contains approximately 34.of the amount required to .form the normal type.

v Erma: 4 Solution A Pounds Water 1,200 Aqueous solution 25% of causticsoda- 288 Tall oil (said No. 160) 200 Solution B Pounds Copper acetate(32% copper)---- 153 Water 800 Solution C Pounds Solvesso" #3 apetroleum solvent) 800 In the dehydratin process sumoient "Solvesso" isremoved to yield 408 lbs. or a csition containing approximately 63% ofthe hydroxy copper soap-12% copper.

The composition represents a dispersion of hydroxy copper tallate in avolatile solvent vehicle the normal compound would require. On apercentage basis it contains approximately 89% of the amount required toform the normal coppertallate soap.

Solution A Pounds Water 900 Flake caustic soda (76% N) 60 Tall 01 250Anti-oxidant (alipha-naphthol) 3 After the dehydrating process, theweight of the composition is adjusted to 470 lbs. The composition thencontains approximately 76% hydroxy copper soap-10% copper. The productreprts a dispersion of a mixed hydroxy copper tallate-naphthenate soap,in a volatile vehicle. The formula contains only 61% of the amount oftall oil-naphthenic acid required to form the normal copper soap.

PLE 6 Solution A Pounds Water 2,000 25% aqueous solution of caustic soda350 Solution B Pounds Water 1,500 Copper sulfate (25% copper) 285Solution C Pounds Petrolatum 850 Naphthenic acid (acid-No. 220) 200After the process of dehydration, the weight of the composition isadjusted to 46 0 lbs. This composition which is in paste form representsa dispersion 0! hydroxy copper naphthenate in a non-volatile vehicle.The metal content of this paste is approximately 15%. This formula conle formula contains 309 lbs. less tall oil than mm; only 36% of theamount acid yvhich would be required to form the normal copper soap.

Exams: 7

1000 lbs. or a hydroxy copper naphthenate dispersion paste, prepared asdescribed in Example 1, are commingled with: v

2000 lbs. of a mineral spirits solution of normal copper naphthenate,such solution carrying 9% copper content.

There is thus obtained 3000 lbs. of a composition representing acombination oi! a hydroxy copper soap with a normal copper soap-thetotal copper content of this formula being approximately 12%.

' Exmm 8 500 lbs. of a hydroxy copper soap, obtained as described inExample 2,' is commingled with:

50 lbs. 01' normal mercury compound 01' mercury content. A

This process yields 550 lbs. 0! a composition representing a combinationof a hydroxy copper soap with a normal mercury compound.

Solution A Pounds Water 800 aqueous solution of caustic soda. 250 Oleicacid (acid No. 195) 200 Solution B Pounds Water 1,200 Lead acetate (54%lead) 300 Solution C Pounds Mineral spirit: 500 Petroleum res In the prc o i smllcient zyloi is remover; so yield 250 lbs. of end. product.This represents mobile diaper clan of mixed copper zinc hydroxy soap invehicle. The metal contents are approximately:

Percent Copper re Zinc 4 This formula contains only 64% of the acidwhich would. be required. to form the normal soaps.

EXAMPLE 10 Solution; A I

Pounds Flake caustic soda so Water 1,100

Naphthenic acid (acid No. 2 20) 220 Hydrogenated rosin (acid No. 160) 10Solution 5 Pounds acetate (54% lead) 428 Water 1.200

Solution C Pounds Hi h flash na htha 400 The weight of the end productobtained after dehydration is adjusted to 770 lbs. This compositionrepresents a dispersion of hydroxy lead soap or two acids in a volatilevehicle. The metal content of this formula is approximately 30% lead.The formula contains only 48% 01" the full amount 01' acid which wouldbe required to form the normal soap.

After the process or dehydrating, the weight or the resultantend producti adjusted to 650 lbs. The composition represents a dispersion ofhydroxy lead oleate in a vehicle. The lead content of the formula is26%. This formula contains only 45% 01 the full amount of acid requiredto produce the normal lead soap.

Exsuw: 12

Solution A Pounds Water 200 Caustic so 57 Naphthenic acid (acid No.230).; 1st

Solution B Pounds Cobalt sulfate crystals (20% cobsltitilt? Winter 800Solution C Mineral spirit Neutral rosin oil 200 After tlehydrationftheweight of the em'i mod not is adjusted to 8&5 lbs. The compositionrepresents a dispersion of hyolrmzy cobalt hash, thenate in 2. vehicle.content is proximately 5%. This formula contains 53% less acid thenormal cobalt haphthenate would rec aim.

EXAMPLE 1E3 Solution A.

Pounds Water use 10% aqueous solution of caustic soda ass Tall oil (acidNo. 160) z-ethylhexoic acid (acid No. soc) 100 Solution 23 Pounds Ironsulfate (20% iron) 21?. Water 600 Solution C V Pounds Xylol 500 Afterthe dehydration process, the weight of the resultant end product isadjusted to 525 lbs. This composition represents a dispersion of hydroxyiron soap in a volatile vehicle. The metal content is 8%. This formulacarries only 55% of the full amount of acids required to form the normaliron soap.

aeeaseo resents a mixture of hydroxy manganese naphthenate-benzoate in avolatile vehicle. The metal content is This formula contains only 75% ofthe full amount of acids required to obtain the normal manganes soap.

EXAMPLE Solution A Pounds Water 1,200 Aqueous solution of caustic soda,25% concentration 233 SoZutionB I Pounds Copper sulfate crystals 190Water 700 Solutions A and B were commingled under agitation. The copperhydroxide which was formed precipitated out in the form of awater-insoluble magma. This was then commingled with Solution C whichcomprises:

Pounds Sovosol 200 Naphthenic acid (acid N0. 210) 129 The weight of theend product after dehydrating was adjusted to approximately 264 pounds.The end product represents a dispersion of hydroxy copper naphthenate ina volatile vehicle. The formula contains 70% of the hydroxy coppernaphthenatel8% copper. The composition carries only 83% of the amount ofnaphthenic' acid which would be required to form the normal compound.

The various hydroxy soaps to which I have referred may be used for awide variety of purposes. For example, and without limitation, they maybe employed as fungicides, as active ingredients in anti-fouling shipbottom paints, as insecticides, as mildewproofing agents, as catalyticagents, as paint and varnish driers, ink driers, linoleum compositiondriers, as agent to prevent loss of drying on ageing of paints and othercoating compositions, as wetting agents, etc. I

The metal soaps produced, as hereinbefore described, may be used as thesole metallic soap constituent of other compositions as stated, or maybe used in combination with other metallic soaps in such compositions.For example, as a fungicide it may be desirable to employ a combinationof normal. copper naphthenate and my hydroxy copper naphthenate. It ispossible for this purpose to mix together copper hydroxy soapdispersion, produced as hereinbefore described, with a normal coppersoap either in the same or in difierent quantities as may be desired.Such a mixture may then be further associated with other ingredients toform, for example, a treating medium for the fungicidal-water-proofingand flame-proofing treatment of textiles.

Another combination which has been found to be of considerable utilitycomprises a mixture of the hydroxy lead naphthenate dispersion of thisinvention with other metallic naphthenates prepared by conventionalmethods, e. g., it may be desirable to incorporate into a coatingcomposition, such as a paint, a plurality of metal soaps which mayinclude my hydroxy lead naphthenate dispersion and cobalt naphthenateand manganese naphthenate made by conventional methods.

Having thus fully described the invention, What I claim as new anddesire to secure by Letters Patent is: i

1. Process of producing a dispersed hydroxy heavy metal soap in adehydrated organic vehicle, which comprises: thermally dehydrating in asub stantially water immiscible organic vehicle an aqueous magmacomprising the reaction product of an alkali soap or at least onesubstantially water-insoluble non-volatile organic acid, free alkalihydroxide and a sufilcient quantity of wetter-soluble salt of at leastone heavy metal to completely react with the alkali soap and the freealkali hydroxide, whereby said hydroxy heavy metal soap is finallydispersed in substantially insoluble form in said dehydrated organicvehicle.

2. Process of producing a dispersed hydroxy heavy metal soap in adehydrated organic vehicle, 1mm comprises: thermally dehydrating in asubstantially water immiscible organic vehicle an aqueous magmacomprising the reaction product of an alkali hydroxide and a sufiicientquantity of at least one water-soluble heavy metal salt to completelyreact with the alkali hydroxide, there befijg present in said vehicleduring said dehydratii step a quantity of at least one substantiallywater-insoluble non-volatile organic acid in an amount insufllcient toproduce the normal salt of such heavy metal but sufficient to producehydroxy metal soap, whereby said hydroxy heavy metal soap is finallydispersed in substantially insoluble form in said dehydrated organicvehicle.-

3. Process of producing a dispersed hydroxy copper soap in a dehydratedorganic vehicle, which comprises: thermally dehydrating in asubstantially water immiscible organic vehicle an aqueous magmacomprising the reaction product of an alkali soap of at least onesubstantially water-insoluble non-volatile organic acid, free alkalihydroxide and a sufficient quantity of a water-soluble copper salt tocompletely react with the alkali soap and the free alkali hydroxide,whereby said hydroxy copper soapis finally dispersed in substantiallyinsoluble form in said dehydrated organic vehicle.

ARTHUR IWINICH.

